2,::(I) 159 Shi [11 ] ;, [ 8 ] (4) ( NonEquilibrium Greenπs Func2,,,,,,, [12 ] [ 13 ] [14 ] [15 ] [ 16 ],,,,,,,,,,,,,,, [1,2,3,4 ], ( Adiabatic Ap2 pr

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1 PRO GRESS IN P H YSICS Vol. 28 No. 2 J un. 28 :12542 (28) : ( I), (,, 119) :,,,, : ;;; ; :O469 ;O561 ;O64 :A,,,,, : (1) ( ) ( SPM), [6 ] ;, [7 ] ;,,,, [8 ] (2) (),, (),, Hu,, [ 9 ] ;, [ 1 ] (3),,, [15 ], : : ( , , 63211, ) 973 (26CB8622, 26CB92135)

2 2,::(I) 159 Shi [11 ] ;, [ 8 ] (4) ( NonEquilibrium Greenπs Func2,,,,,,, [12 ] [ 13 ] [14 ] [15 ] [ 16 ],,,,,,,,,,,,,,, [1,2,3,4 ], ( Adiabatic Ap2 proximation) ( Density Function Theory, DF T) ( Pseudopotential) tion, N EGF) ( Density Functional Theo2 ry) [17,18 ] Thomas2Fermi,,,,, 2, Thomas [ 19 ] Fei2 mi [2 ] ;,Dirac [21 ] Wigner [22 ] 1951 Slater 1/ 3 [23 ], Hatree2Fock2Slater ( X),,, 1964 Hohen2 berg Kohn [24 ] 1965, Kohn Sham [25 ], Hohenberg Khon Sham, [18 ], (Local Density Approximation),,,, [18 ],,, ,,,, ^H n = En n ( R, r) r, R, En n, n ( R, r) n, ^H, ^Te = - h 2 ^T N = - j 2 M j h 2 j 2 m 2 r i, 2 R j,

Fei2 mi [2 ] ;,Dirac [21 ] Wigner [22 ] 1951 Slater 1/ 3 [23 ], Hatree2Fock2Slater ( X),,, 1964 Hohen2 berg Kohn [24 ] 1965, Kohn Sham [25 ], Hohenberg Khon

3 16 28 ^V e e = i, i e 2 8 ri - ri ^V N N = = j, j, e 2 Zj Z j 8 Rj - Rj, ^V en = = i, j e 2 Zj 4 ri - Rj,,,,,, :, ;,,,, (Born) (Oppenheimer) 1. 2 Thomas2Fermi,,, Thomas2Fermi ( 1927 ) Thomas [ 26 ] Fermi [27 ] ,,,, (LDA) T TF [ ] = C K ( r) 5 3 d r, C K = 3 1 (3 2 ) Hartree Dirac [28 ] Slater CX = 3 4 EX [ ] = - CX ( r) 4 3 d r, 1/ Hartree 3, EC [ ] = ( r) 3 4 d r ( r) 1 3,Thoms2Fermi2Dirac, ETFD [ ] = CK ( r) 5 3 d r ( r) ( r ) r - r d r ( r) ext ( r) d r +,,,, DF T 1. 3 Hohenberg2Kohn 1964 Hohenberg Kohn [29 ],, :,,, Hohenberg2Kohn, ( r), : ( r), ( r), ( r) d r = n, E[ ( r) ] E, E,E = Min E[ ] 1. 4 Kohn2Sham Hohenberg2Kohn, P. Hohenberg W. Kohn,,, 1965, W. Kohn L. J. Sham, [18 ] W. Kohn L. J. Sham

871 Hartree Dirac [28 ] Slater CX = 3 4 EX [ ] = - CX ( r) 4 3 d r, 1/ 3. 739 Hartree 3, EC [ ] = -. 56 ( r) 3 4 d r.

4 2,::(I) 161,, (Local Density Approximation, LDA) TFD,,,, : D. M. n Ts [ ] = i = Ceperley B. J. Alde i - 2 i [ 3 ],J. P. Perdew Alex F[ ]: F[ ] = Ts [ ] + J [ ] + Exc Zunger [31 ] 1 [ ], Exc [ ] T[ ] - Ts [ ] + Vee[ ] - J [ ] J [ ] Exc [ ] X ( rs) = rs, T T s, E [ ] E[ ] = Ts [ ] + J [ ] + EXC [ ] + V ( x) ( d x Kohn2Sham,Kohn2Sham C ( rs) = rs = A + B rs + Cln rs + D rsln rs rs 1 / (1 + 1 rs + 2 rs) rs > n i ( x) - i =1 = ( x1 ) ( x2) i ( x) dx + 1 2r12 d x1 dx2 + EXC [ ] + V ( x) ( d x { i} Kohn2Sham : ^H ks i -, V ef f V ef f ( x) i ( x) = i i ( x) ( x) = V ( x) + ) r - r Ex c [ V xc ( x) = ], ij = i ij ( x) ( x dx + V x c ( X), Exc [ ], Kohn2Sham ( r) E[ ] 1 E[ ] = i = n 1 i - 2 ( r) ( r ) d rd r + EXC [ ] r - r - V ( r) ( d r,kohn2sham W. Kohn L. J. Sham, Ex c, 1. 5, : X C X Dirac C rs 1 rs > 1 ( U) ( P) A U = B U = C U =. 311 D U =. 2 A P = B P = C P = D P =. 7 U = U = U = P = P = P =. 2611, (U) ( P),,,,, ( Generalized Gradient Approximation,

$( d x { i} Kohn2Sham : ^H ks i -, V ef f 1 2 2 + V ef f ( x) i ( x) = i i ( x) ( x) = V ( x) + ) r - r Ex c [ V xc ( x) = ], ij = i ij ( x) ( x dx + V x c ( X), Exc [ ], Kohn2Sham ( r) E[ ] 1 E[ ] =$

5 GGA), : Per2 dew Wang 1991 ( PW91) [ 32 ] ; Perdew,Burke Ernzerhof 1996 ( PB E) [33 ] ;Becke 1988 (B88) [34 ] ;Lee, Yang Parr 1988 (L YP) [35 ],, 1. 6,, Kohn2Sham,,,, [36 ] ( PA W) [37 ],,, ^H Ec, Kohn2Sham Kohn2 Sham,,, c,, Ev v H v = Ec v H v= E v v v = v ps + A vc c v ps C v c, A vc = - c v ps ^H v ps,,, : VASP [41 ] ABIN IT [ 42 ] ^H v ps = ^H v - A vc v c ( Fireball Basis Set) = Ev v = Ev v ps c - c - c ^H v c v ps E v v c v ps +, ( Ev - Ec ) c c,, [38,39 ] [4 ], David Vanderbilt 199 ( Ultrasoft Pseudopoten2 tial) [4 ],,, 1. 7, [43,48 ] l m ( r - R) = Rl ( r - R ) Y l m Ec c c v ps l m, Rl, Y ( ^H + ( Ev - Ec) c c ) v ps l m, r, R c v ps :

VASP [41 ] ABIN IT [ 42 ] ^H v ps = ^H v - A vc v c ( Fireball Basis Set) = Ev v = Ev v ps c - c - c ^H v c v ps E v v c v ps +, ( Ev - Ec ) c c,, [38,39 ] [4 ],

6 2,::(I) 163,, SZ DZ TZ,SZP,DZP TZP TZDP TZTP TZTPF 1. 8 Kohn2Sham Kohn2Sham, Kohn2Sham, Kohn2Sham ( r) = E( r) 2 + d r n ( r ) r - r + V ion2el ( r) + V xc [ n( r) ] V ion2el ( r) Ezc [ n( r) ] V ex t ( r),v xc ( r) = n( r) H l E, l H E - 1 l, c, nv ( r) G R = Hc, E l H c, E c H c, E r - - l r nc ( r) H r, E c H r, E r, V ion2el ( r) V nl ( r,, i r r ),, KS,,, = l Hl E, l- 1 gl R H l E, l+1 VASP [ 41 ], SIES2 TA [44 ],Gaussian [ 45 ], WIEN [ 46 ] VASP = r H r, E r+1 g R r H r, E r- 1,,, PAW VASP, Gaussian, Gaussi2 g R l g R r : [49 ] [5 ] an,3 G < G < G < = G R < G A G R, SIESTA,Hartree WIEN,,,,, 1. 9,, Kohn2Sham,, [47,48 ] G R,,,,,,, G A,

( r) = n( r) H l E, l H E - 1 l, c, nv ( r) G R = Hc, E l H c, E c H c, E r - - l r nc ( r) H r, E c H r, E r, V ion2el ( r) V nl ( r,, i r r ),, KS,,, = l Hl E,

7 n = - i d E 2 G< = - i d E 2 < GR G A a = - i d E 2 < GR < G A - eq i d E 2 GR = neq + nne q neq = - i d E 2 GR = i d E 2 GR f < eq GA A - R = - i d E 2 f ( G A - G R ) - nnep = - i d E 2 < GR neq GA G A < neq GA 1 d Ef Im ( GR ) = - i d E 2 GR ( i ( f l - f ) l + i ( f r - f ) r ) G A = d E 2 ( f l - f ) G R l G A + d E 2 ( f r - f ) G R rg A l, r min = min ( l, r ) max = max ( l, r ), f min f max f f min n = 1 d Ef min Im( GR ) + d E 2 ( f max - f min ) G R i G A I,,,1 neq,, ( 1 Emin min ) nne q,,,, ( 1 min max ) 1,,, T I T ( E) = T r[ l ( E) G R ( E) r ( E) G A ( E) ] I = 2e h d E( f max - f min ) T ( E) 1. 1 STM ( Scanning Tunneling Micros2 copy) [51 ] 1982,,, STM ( d I/ dv ) (d I/ dv Mapping) ( STM2IETS) [52 ], ( d 2 I/ dv 2 spectroscopy) (d 2 I/ dv 2 Mapping),,, Landauer2B ttiker, Tersoff2Hamann [53 ], Chen Bardeen [54 ],Joachim ( Elastic Scat tering Quant um Chemist ry, ES2 QC) [55 ] Tersoff2Hamann,, Bardeen,, Bardeen,Chen, Bardeen ESQC,, STM :, ;, ;,STM ;,

min f max f f min n = 1 d Ef min Im( GR ) + d E 2 ( f max - f min ) G R i G A I,,,1 neq,, ( 1 Emin min ) nne q,,,, ( 1 min max ) 1,,, T I T ( E) = T r[ l ( E) G R ( E) r ( E) G A ( E) ] I = 2e h d E(

8 2,::(I) 165 STM STM,,,,, STM,, STM,,,,, (2) : (i) Tersoff2Hamann [57 ],, (ii) Bardeen [ 58 ],, (iii) Landauer2B ttiker [59 ],, (iv) Keldysh ( nonequilibrium Greenπs f unction approach) [6 ],2, 2 (i) Tersoff2Hamann Tersoff2Hamann,, Bardeen,, (1) STM,, I (V ),STM F +ev ( r, E) d E E F Si (111)27x7 STM, EF, ( r, E), ( r, E) = i ( r) 2 ( E - Ei) STM, STM, Pt, Ir, Pt Ir NaO H i E i (ii) Bardeen,, 21 nm [56 ] I = 4e, g s ( EF - ev + E) T ( EF + E) M 2,, g 2 M = - 2 m v - 3 v ) STM,, V Tersoff2Hamann,, M, (iii) Landauer2B ttiker [ 61 ], Landau2, er2b ttiker,,,,1 G = I = e2 I V bins h R 2e2 h T,, I (V bias ) = 2e T ( E) d E h ev bias,,, STM, DF T z,,, (iv) Keldysh ( non2 equilibrium Greenπs f unctio n app roach) 2 2,Hamitonian H = k, L, R kc + k+ Hint ({ d + n } ;{ dn} ) +

Bardeen,, 21 nm [56 ] I = 4e, g s ( EF - ev + E) T ( EF + E) M 2,, g 2 M = - 2 m v - 3 v ) STM,, V Tersoff2Hamann,, M, (iii) Landauer2B ttiker [ 61 ], Landau2, er2b ttiker,,,,1 G = I = e2 I V

9 (V k, nc + kd n + H. c. ) k, L, R,,,,,, Landauer 2 B ttiker 1. 11,,,,,,,,, DF T,,,,,, (Molecular Mechanics, MM) 197, (Born2Oppenheimer app roximation),,,,,,,,,,,, ( r N ) = angles V n 2 ki 2 ( ri - ri, ) 2 ki + bonds N N ij i = 1 j = i+1 (1 +cos( n- ) ) + ij 4 r ij 12 - ij 6 r ij angles 2 ( i - i, ) qiq j 4 rij,,,, ki, ri r i, i,, ;,, i i, i,;, V n,;,,,, LJ MM [6264 ] AM2 B ER [ 65 ] CHARMM [ 66 ] MM MM Allinger, MM2 [62] MM3 [63] MM4 [64] : U = U nb + U b + U+ U+ U+ U el + U cross U nb ( r) = a - / r - b ( / r) 6 U b ( r) = kb 2 ( r - r ) 2 [1 - k b ( r - r ) - k b ( r - r ) 2 - kgb ( r - r ) 3 ] U( ) = k (- ) 2 [1 - k (- ) - 2 k (- ) 2 - kg(- ) 3 ] 3 2 V n U( ) = (1 + cosn n = 1 ) U( ) = k (1 + cos2 ) U el ;U cross,

n- ) ) + ij 4 r ij 12 - ij 6 r ij angles 2 ( i - i, ) 2 + + qiq j 4 rij,,,, ki, ri r i, i,, ;,, i i, i,;, V n,;,,,, LJ MM [6264 ] AM2 B ER [ 65 ] CHARMM [ 66 ] MM MM Allinger, MM2 [62]

10 2,::(I) 167,,,,,,,,,,,,,,,,, L EED, STM,,,, ;,, 2 Ag [ 5 ],Ag (C22 H14 ),OTFT [6773], Si2 TFT [72,73], [6778],,, (MB E) (L EED) [81 ] Ag (11) L EED Ag (11), 2 L EED 14,L EED, Ag (11) 145,L EED ( 2a2 f), Ag (11), ( 2f), 2 (d), Ag (11),;,, (2 (g) ), Ag (11) [ 83,84 ], 14, 14 (2 (f) ),, 145,,L EED ( 2 (i) ),,, [82,84 ] 145,,, L EED (3 (a) ), 3 ( b) ( b1, b2 ) ( a1, a2 ) Ag (11) a1 = !, a2 = 4186! Ag (11) 3 (b), Pentacene = Ag (11), b1 = ! b2 = !,= , b1 a1 =

Ag (11) [ 83,84 ], 14, 14 (2 (f) ),, 145,,L EED ( 2 (i) ),,, [82,84 ] 145,,, L EED (3 (a) ), 3 ( b) ( b1, b2 ) ( a1, a2 ) Ag

11 Ag (11) L EED : (a) E = 13 ev, Ts = 2, Tv = 145, t = 2 s ; (b) E = 13 ev, Ts = 2, Tv = 15, t = 3 s ; (c) E = 13 ev, Ts = 2, Tv = 151,t = 4 s ; (d) E = 13 ev, Ts = 2, Tv = 152,t = 5 s ; (e) E = 13 ev, Ts = 2, Tv = 153,t = 6 s ; (f) E = 13 ev, Ts = 2, Tv = 154,t = 65 s ; (g) E = 34 ev, Ts = 2, Tv = 154, t = 65 s ; (h) E = 13 ev, Ts = 14 ; (i) E = 13 ev, Ts = 145, Cu ( 11) [78 ] Si (1) [79 ],Ag (11) [ 8 ], Ag (11), Ag (11),L EED,,,,,,,,, Ag(11),Ag, Ag, Ag,, Ag,,, Ag, Ag MM2 MM +, MM + Ag (11), Ag [85 ], Ag (11), ( 4 (c) ) ( 4 (a) ),, ( 4 (b) ), ( ) Ag 5!, 3 Ag (11) : (a) 34 ev L EED ; (b), b1 = 3 a1 - a2, b2 = - a1 + 4 a2, b1 = !, b2 = !

= 13 ev, Ts = 14 ; (i) E = 13 ev, Ts = 145, Cu ( 11) [78 ] Si (1) [79 ],Ag (11) [ 8 ], Ag (11), Ag (11),L EED,,,,,,,,, Ag(11),Ag, Ag, Ag,, Ag,,, Ag, Ag MM2 MM +, MM

12 2,::(I) 169,Ag, ( Esp) ( Eopt ),, 4(d)4(e),,, 2U (Ag ), : [1] (4(d) ) ; 2U, 2L ( ) (4(e) ),,, Ag(11) 5 5, Ag (11) A, B, C Db1, b2 Ag(11) L EED ( 5 (a) 5 (b) ) 5!, A B

13 17 28 A C ( 5 (c) ),B D ( 5 (d) ) A B, 3. 3! C D Esp Eopt A B,3. 3!, C D Ag (11) L EED, 5 % L EED,,, Ag (11),, Ag (11),2U,,, 3 : P TCDA DMe2DCNQ I Ag [ 8 ] Ag (11), 2 2,, [15 ],, ( ), SPM ( ),,,,,,,,,,,(), PTCDA DMe2DCNQI( 7 (a), (b) ), Ag(775) ( (111) (221) ),Ag Ag(775) PTCDA (111), DMe2DCNQI (221), [8] PTCDA,PTCDA,, NIXSW K X2ray [8688] 6 P TCDA DMe2DCNQ I Ag (775) STM,. 8 V,. 1 na (a) 5 nm 5 nm, P TCDA DMe2DCNQ I STM,DMe2DCNQ I, PTCDA (111) (),DMe2 DCNQ I (221) (),() ; (b) 3 nm 3 nm,ptcda/ (111) DMe2DCNQ I/ (221) STM

14 2,::(I) 171 Ag (775),(111) (221) Ag (775),3334 K, P TCDA (111) DMe2DCNQ I (221),STM 6 (a) (b), P TCDA (111), DMe2 DCNQ I (221),,,,Ag (111), PTCDA DMe2DCNQI,,,,,, Ag (111),, Ag, Ag ( 111) Ag (221), (DF T) VASP [41 ], ( General Gradient App roximation ( GGA) Func2 tional) PW91 [32 ],( Ultra Soft Pseudopotential, U SPP) [4 ] 2, Kohn2Sham ( PW), Monkhorst2Pack k, Blochl Linear2Tetrahedron,, k. 2 ev, 4 ev,, 1 nm,ag P TCDA DMe2DCNQ I 7 P TCDA (111) (221) (. 54 ev,. 22 ev) ;DMe2DCNQ I (221) (111), ev ev, (221) P TCDA, DMe2DCNQ I,. 1 ev,,(221) ( ) e 4, 6 1,,P TCDA, DMe2DCNQ I (221),DMe2DCNQ I P TCDA, P TCDA N TCDA, ( 7),,(111), (, 3! ),,,,,, 7, O N,,, [ 8688 ] [ 89 ]P TCDA,, [ 87 ] P TCDA Ag (111) C, N EXA FS C 2. 86! P TCDA/ Ag (111),C O,

Linear2Tetrahedron,, 2 2 1 k. 2 ev, 4 ev,, 1 nm,ag P TCDA DMe2DCNQ I 7 P TCDA (111) (221) (. 54 ev,. 22 ev) ;DMe2DCNQ I (221) (111), 1. 46 ev 1. 36 ev, (221) P TCDA, DMe2DCNQ I,.

15 C, !, 2. 86! [ 87 ]C,C,P TCDA Ag (111) P TC2 DA,. 2 ev, [89 ],, 7 PTCDA DMe2DCNQ I Ag (111), [88 ]X P TC2 DA/ Ag (111) C, P TCDA Z + 1P TC2 DA/ Au (111) P TCDA X,( 8), 8 ( ) ( ) C X : (a) ; (b), ;,,,,,,, 4 QA Ag [ 11 ] Ag (775),,,,,, Ag (L UMO) Ag 4 d2 [ 9 ], L UMO Ag d, Ag, DMe2 DCNQ I P TCDA CN CO [8 ],,,

16 2,::(I) 173, (QA), [9193 ] QA (OL EDs) [ 9497 ] QA N QA nc, 9 (a), n,, [98 ] ( HO P G) QA nc [ 95,96,98,99 ], 2,,, ;,,,,, Ag (11) QA nc ( MB E2L EED) QA4C QA16C, (DF T) (MM) QA nc Ag (11) ( STM) 9 (c)2(f) QA4C Ag (11) L EED L EED 9 (c). 2 ML,L EED. 5 ML, L EED (9 ( d) ). 8 ML, L EED, 9 (e) L EED 9 (f), () ( ) () Ag (11), [ 5,16 ] Ag ( 11) a = !,b = ! 9 (f ) QA4C Ag (11) QA4C = 6 4 Ag (11),QA4C a1 = 6 a = !,b1 = 4b = !, 1 = 9 QA16C,, L EED, 9 ( g)2(j),. 2 ML,. 5 ML,. 8 ML 9 ( h) QA16C Ag (11), Q4AC = a2 = 3 a - b = !, b2 = 5 a + 6b = !, 2 = (a) (QA) ; (b) QA M1C ; (c) (d) (e) (f) QA4C Ag (11) ML L EED ; (g) (h) (i) (j) QA16C Ag (11) ML L EED L EED, QA4C QA16C,,,, L EED QA nc, DFT, MM QA,

9 (f ) QA4C Ag (11) QA4C = 6 4 Ag (11),QA4C a1 = 6 a = 17. 337!,b1 = 4b = 16. 345!, 1 = 9 QA16C,, L EED, 9 ( g)2(j),. 2 ML,. 5 ML,. 8 ML 9 ( h) QA16C Ag (11), Q4AC = 3-1 5 9 a2 = 3 a - b = 9.

17 174 28, Ag,O C [ 8 ] QA4C QA16C M1C ( 9 (a) ( b ) ) (DF T) VASP, ( GGA) PW91 ( Perdew2Wang 91 f unctional), PA W ( Projector Augment Waves) 2,Kohn2Sham ( PW), QA1C M1C O Ag,QA4C QA16C O Ag STM Ag M1C Ag (11),6 4 Ag (11), 1 (a),ori21 Ori26,O Ag 1 (a), 1. 5 ev O Ag, Ori23 1 (b) Ori23,, O,,,O Ag, DF T L EED Ag (11),, (11),, [5 ] 1 Q1MC/ Ag (11) : (a) ; (b) Ori23, DF T, 1 Ori23, QA nc, n , ; 11 (a), n = 4, n = 16 18Ag (11), 11 (a), n = 6,Ag, n = 4 36, n = 6 15, n = 8 18, n 8 18 n = 8, [1 ] Ag (11), QA nc 11 (b) Ag, QAnC Ag

5 ev O Ag, Ori23 1 (b) Ori23,, O,,,O Ag, DF T L EED Ag (11),, (11),, [5 ] 1 Q1MC/ Ag (11) : (a) ; (b) Ori23, DF T, 1 Ori23, QA nc, n 4

18 2,::(I) 175,,DF T MM, C (M4C, 11 (c) ), Ori23, 11 (d) 12 (d),,,stm : a2 = 9. 77!, b2 = 29. 3!,= 84. 7, STM : a2 = 1. 1!, b2 = 29. 9!, = 82. 3, 5 % 11 QA nc : (a) ; ( b) MM QA nc Ag ( 11), n = 4, 6, 8, 12 ; (c) M1C M4C ; (d) DFT M4C DF T (M4C) MM (QA4C), C, DF T MM QA4C QA16C Ag (11), 12 (a) ( b) QA4C Ag (11) STM 12 (c) 1. 3 V STM 12 (c) STM [8,11 ] : a1 = !, b1 = !, = 9 ; STM : a1 = 18.!, b1 = 16. 5!, = %,, QA nc M1C, QA nc QA16C STM 12 STM STM : (a), ( b) QA4C QA16C Ag (11) ; (c) QA4C STM, ( STM ) STM ( ) ; ( d) QA16C 77 K STM ( b). 4nA,. 8 V,1 nm MBE2L EED STM QA4C QA16C Ag(11), 5 FePc Kondo [16 ], [5 ],,, ( Kondo effect)

Ag (11) STM 12 (c) 1. 3 V STM 12 (c) STM [8,11 ] : a1 = 14. 68!, b1 = 16. 67!, = 9 ; STM : a1 = 18.!, b1 = 16. 5!, = 91.

19 [11 ] 1998, ( STM) [12 ] [13 ] Fano,, ( ) ( mev ),,,, [ 14 ], [ 15 ], [ 16 ],, (iron phthalocyanine, FePc) Au (111) 2,, Fano,Au (111) Fe ( 6 K) [ 17 ] Au ( Fe) ( 1 K) [ 18 ],, 13 Au (111) STM, STM Fe d [ 19 ] Au (111) ( ), [ 1 1 ][ 112 ] 15 di/ dv I (14 (a) ), (14 ( b) ) (14c) I,,,76 mev 23 mev,,, 86 mev 23 mev 14 (c) Fe2I Fe2II Fe d 23 Fano [11 ] 13 FePc Au (111) STM 1 nm 1 nm,u = 5 V, I = 69 pa. Au (111), 1/ 2 14 d I/ dv (a) (b) a b d I (V ) d (V ) = A ( + q) B, = ( ev - ) /, A, B d I/ dv, q Fano, Fano, Fano Fano :1) () d ;2) d (14 (c) ) ;3) ;4), Fano,, 2 K, STM Fano kb T K = T K T K = K, T K = K

mev 14 (c) Fe2I Fe2II Fe d 23 Fano [11 ] 13 FePc Au (111) STM 1 nm 1 nm,u = 5 V, I = 69 pa.

20 2,::(I) (a) FePc d I/ dv (),,Fano, q = , = mev,= mev ; (b) FePc d I/ dv (),,Fano,q = , = mev,= mev ; (c) d I/ dv, Fe2I Fe2II Fe 3 d, SS2I SS2II Au,FR2 FR2 Fano FePc Au (111) (DF T) VASP, ( GGA) PB E ( Perdew2Burke2Ernzer2 hof) [33 ], PAW ( Projecto2 raugment Waves) 2,Kohn2Sham ( PW),4 ev, c(7x8),, ( 28,FePc 57 ),,, ev/! 8,15,b a 14 mev, mev, VASP LDA [31 ] SIESTA B3L YP [34,35,44 ],PB E, 15 (a) 15 (b), I III Fe, II Fe STM 1/ 2, Fe ( spin polarized partial density of states,sp2pdos),( ) ( ),, 1. 9 B, Au (111) Fe Au ( Fe) [17,18 ], Fano Au (111), :Au (111) d2 Co Pc,28 K [5 ] ;Cu (111) Co (CO) 4, 283 K [4 ] ;Co. 1 % 5 nm Cu/ Cu (111),45 K [111 ] ;Ag (111),29 K [13 ],,, Au (111) ( 5 K) Au (111) (7 K), 28 K [ 12,15 ], Fe,Au2Fe, ( 15 (c), (d) ),, Fe

21 Au,Fe Au ;, Fe Au,Fe Au,, ( 15 (c), (d) ),, [13,14 ] Au ( 111), 6 STM [112 ] 15 Fe Au SP2PDOS (a) ; (b) ; (c) Fe SP2DOS ; (d) (a) 1 Au SP2DOS ; (e) (b) 2 3 Au SP2DOS ; (f) II Fe 2 Au SP2DOS( m = ) Fano Fano, d I/ dv q FePc/ Au (111), d, q q ( q = 2. 2) q ( q =. 12),,Fano, Fano, [113,114 ] 1982 ( STM), STM STM [ 115,116 ] [ ], STM, STM,,, [12,121 ], (L T2STM) DF T (11), ( ), 395 K, Ag (11)

22 2,::(I) 179 [8,122 ] (ML) ,. 6 ML Ag (11) perylene/ Ag (11) 2, VASP,GGA2PW91,,, 4 ev 6 6,perylene,Ag (11), 6 6 Ag,,, STM, perylene,, Ag (11), perylene STM Hamiltonian,, STM [6 ], W, perylene W (1),,,, STM, STM 2,, 2,,,. 3 ev,, 16 (a), Ag (11),(11) [ 11 ] ev, [ 8 ] (11) (16 ( b) ) (16 (c) ), 16 (a) perylene (11) (b) (11) perylene (c) perylene ( -. 7 ev +. 7 ev) 17 ( a) STM 4,1. 5! STM (17 (c) ) STM,, 17 (c) 16 (b), Ag (11) (),L EED Ag(11),,,

23 18 28, (11) d,,, STM, 17 (11) perylene (a),3 nm 3 nm( b) (a) perylene,1. 2 nm 1. 2 nm(c) STM :V = V, I = 9 pa (1),, - 8 ev, - 1 ev [123 ],- 2 ev,, STM, STM,STM 18 (a)2(c) (11) perylene STM, (d)2(f) (a)2(c), (g)2(i) STM (d)2(f) 18 (a) STM (i) perylene (11) ( -. 8 V, pa), : (a) 1 nm 1 nm,. 5 ML,V = -. 8 V, I = pa (b) 7. 9 nm 7. 9 nm,. 6 ML,V = V, I = pa (c) 1 nm 18 (d) 18 (a) 18 (g) 1 nm,. 3 ML,V = V, I = 149 pa STM V pa (18 (b) ),, [1 ] W (1) V,149 pa, (19 (a) ) 19 (b), (, 18 (c) ) 18 (h) (i) 18 (b) (c), STM 18 (h) STM,18 (i) d V V, STM STM

24 2,::(I) (a) perylene W(1) (b) perylene ( -. 7 ev +. 7 ev) 7 [ 9 ] STM, CPU 65 nm, 45 nm,,,,, : ( 2 (a) ) ;( 2 ( b) ),, [ ] 2, [126 ],, -,,,,, ;, 2 ( N EGF2DF T),,,,, [127, ],,,, -,, 1296 [ ] (4,4 bipyridine, 21 (a) )

25 (62alkanedit hiol, 21 ( b) ),,, (1),,,, TransiestaC [136 ], SZP, 21 (1) : top,bridge hollow,,,3 3, 21 (c),, top, (a),.. 9,. 4,,. 39 G, bridge,22 hollow. 1 G [129 ], 4 3 3, 22 (b),, ,. 2,16,, = 1296,, 21 (d),,21 (e), ,. 25 G,. 12 G [129 ],,

26 2,::(I) : (a) ; (b) 1296, S ( E1, E2 ) = E 2 T ( E) d E, E 1, 23 (a) : (1) ev. 125 ev ; (2) ev. 25 ev ; (3) ev. 375 ev ; (4) -. 5 ev. 5 ev,, 23 (b),(a),,,,,,,,: ; ;,, 23 : (a) ; (b) 24 (a2c), 24 (a) ;24 (b), ;24 (c), 1. 5!, 2.!, 2. 5!,, - 2 ev 2 ev

27 184 28, ;,, 24 (a 2b ),, 24 (a2c),,;,, ;,,, 24 : (a2c) ; (a 2c ) 25 (a2c), [137 ] 25 (a) top 25 (b) bridge 25 (c) hollow top bridge,, hollow,,, 25 (a 2c ), 25 (a2c),, top

28 2,::(I) 185 bridge,, hollow,,, 25 : (a2c) ; (a 2c ),. 39 G,. 1 G ;. 25 G,. 12 G. G. 9 G,. 1 G. 5 G, :, ;,,, 8 STM,, STM,,,,,,,,,,

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33 19 28 SELF2ASSEMBLY OF FUNCTIONAL MOL ECULAR STRUCTURES AND PHYSICAL PROPERTIES OF SINGL E MOL ECUL ES : AB INITIO CALCULATIONS BASED ON DENSITY FUNCTIONAL THEORY AND SCANNING TUNNEL ING MICROSCOPY ( ) DU Shi2xuan, GAO Ho ng2jun ( B ei j ing N ational L aboratory f or Condensed M ater Physics, I nstitute of Physics, Chinese A cadem y of Sciences, B ei j ing 119, China) Abstract : Imaging of t he self2assembly growth of low dimensional molecular nano struct ure at a sin2 gle molecular scale, understanding it s formation mechanism, and controlling the configurations and p hysi2 cal properties of t he formed f unctional molecular nanostruct ures, are of importance in t he field of low di2 mensional p hysics and device applications. We review t he self2assembly of f unctional molecules on metal substrates based on density f unctional t heory using ab initio calculations and ultrahigh vacuum molecular beam epitaxy technique. After a brief int ro ductio n of t heory, we p resent t he self2assembled molecular struct ures, interface properties, struct ural controlling,ultimatescanning t unneling microscopy ima2 ging, controlling of t he struct ure and quant um properties of a single molecule. Finally, we give an outlook of t he f unctional molecular nano struct ure formation, t heir p hysical properties, and potential applications by combination of t he experiment s and t he ab initio calculations. Key words : Density Functional Theory ; ab initio calculation ; self2assembly ; electronic structure ; imaging at single molecule scale.

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